Polyolefin asphalt modifiers, methods of modifying asphalt, asphalt compositions and methods of making

ABSTRACT

An asphalt additive comprising a primary rheology modifying component and a secondary rheology modifying component, and asphalt compositions and products having such additive incorporated therein. The primary rheology modifying component is generally a polymer, and the secondary rheology modifying component may comprise a petroleum micro-wax.

RELATED APPLICATION DATA

This application is a Continuation-In-Part of U.S. patent applicationSer. No. 1/311,445, filed Dec. 5, 2011, now issued as U.S. Pat. No.8,784,554, which is a Continuation-In-Part of U.S. patent applicationSer. No. 12/399,960, filed Mar. 8, 2009, now abandoned, both priorapplications herein incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to asphalt compositions, asphaltmodifiers, methods of making and using such compositions and modifiers,methods of modifying asphalt, and asphalt products.

2. Brief Description of the Related Art

Asphalt is a sticky, black and highly viscous liquid or semi-solid thatis present in most crude petroleum and in some natural deposits. In U.S.terminology, asphalt (or asphalt cement) is the carefully refinedresidue from the distillation process of selected crude oils. OutsideNorth America, the product is called bitumen.

Asphalt binder is a key ingredient in pavements, roofing andwaterproofing applications. The primary use of asphalt is in roadconstruction, where it is used as the glue or binder for the aggregateparticles, and accounts for approximately 80% of the asphalt consumed inthe United States. The most common type of flexible pavement surfacingin the United States is hot mix asphalt (HMA) that may also be known bymany different names such as hot mix, asphalt concrete (AC or ACP),asphalt, blacktop or bitumen.

After use of asphalt in road construction, roofing applications, mainlyin the form of roofing shingles account for most of the remainingasphalt consumption. Other uses include waterproofing applications.

Asphalt binder as produced by the refining process does not have thedesired stiffness modulus for heavy load bearing for use in heavilytrafficked pavements such as the Interstate Highways as well as heavilytrafficked inner city streets. Until now polymers such as StyreneButadiene Styrene (SBS) Styrene Butadiene Rubber (SBR), Ethylene VinylAcetate (EVA), Fischer-Tropsch Waxes, Elvaloy Ter-Polymers, Natural andSynthetic Latex and Crumbed Tire Rubber and also combinations of one ormore of these have been used as asphalt binder modifiers.

Over the past seven years or so, traditional Hot Mix has been underscrutiny due to hydrocarbon emissions, energy cost and difficulties incompaction after long hauls and in cold weather paving. A new technologycalled “Warm Mix” asphalt emerged around year 2000 and was promoted bythe National Pavement Association (NAPA) of the USA and this technologygrew very rapidly and a large number of available Warm Mix technologieshave emerged in recent years. Currently there are at least 20 suchtechnologies available to the paving industry and the number is growing.The key benefits of Warm Mix are a reduction in asphalt aggregatemixing, transportation, lay down and paving temperatures by between 30°F. to 70° F. and providing benefits such as drastically reducedemissions during production, drastically reduced emissions duringpaving, energy savings, facilitating longer hauls to paving sites, widerpaving window such as early paving in Spring and later paving into Falland superior compaction over Hot Mix.

Adequate compaction is one of the prerequisites for a long lastingpavement and is difficult to achieve especially with highly modifiedstiff binders as well as with gap graded mixes such as Stone Masticasphalt (SMA) and Open Graded Friction Courses (OGFC). Another challengein achieving adequate compaction is cold climate paving and long hauldistances where the mixing plants are located far from the paving sites.Compaction is considered so important by Federal and State authoritiesthat in many cases contractors are awarded bonuses for achieving thetarget compaction consistently. It is well documented from global fieldtrial and commercial data that Warm Mix applications achieve consistentand on target compaction even in cold weather and with difficult mixes.Also, enhanced compaction through Warm Mix applications a significantdevelopment since stiffer binders are being paved to carry the heavierloads and increasing numbers of vehicles on the roads.

Another major development that has emerged in recent years is the issueof personal heath and the related hydrocarbons exposure to paving crewsand the motoring public. There is a strong movement to reduce suchemissions and Warm Mix technology provides the scope to achieve thetargeted new permissible emissions levels. Also, in the context of GreenHouse emissions, there is a strong movement to limit greenhouse gasemissions by asphalt mixing plants as a contribution to limiting thismajor problem. In Europe the limitations are in place already forcingthe paving industry to use green fuels and reduce usage of fuel makingWarm Mix the technology of choice. In the USA the use of Warm Mix isgaining momentum at an accelerating pace.

The unpredictable surges in fuel cost have made the energy cost ofrunning asphalt mixing plants a severe cost burden. Warm Mix achieves onaverage about a 20% savings in energy cost and this is a substantialreduction aside from the benefits of reduced stack emissions from thereduced volume of fuel required for the same tonnage of output by WarmMix over Hot Mix.

Several technologies are presently in use or in trials or in developmentas Warm Mix technologies and these may be classified into the followingcategories: (a) hard waxes such as Fischer-Tropsch® Waxes; (b)surfactants such as a combination of anti-strip agent and other organicadditives, and surfactants plus water solution; (c) foaming technologiesincorporating hydrated alumino-silicates; (d) foaming technologiesincorporating the use of water either into a portion of the fineaggregate feed (such as the Low Energy Asphalt process) or directatomization of water into the hot binder (such as the Double BarrelGreen process).

A major concern of the Warm Mix process is the risk of moisture damageand this is being studied with earnest to assess this risk potential.Firstly, since Warm Mixes are produced at lower temperatures, thereremains the risk that the aggregates are not completely dried as withHot Mix. Secondly, there is the temptation to push Warm Mix to theultimate limits without any proven data on moisture sensitivity and thismay expose potential such risk even further. Thirdly, the use of wateras the foaming agent is questionable since it has long been establishedthat if water is left on the surface of the aggregate it will reduce theadhesion of the asphalt binder on to the aggregate causing adhesivefailure with time. Also any water present in the binder will reduce thecohesive strength of the asphalt binder over time and cause cohesivefailure.

U.S. Pat. No. 4,267,085, issued May 12, 1981 to Katoh et al., disclosesinjection materials for railroad track beds. Specifically, in a railroadtrack bed an injected layer is formed between the railroad ties and theroadbed so as to protect the latter. The injected layer is composed ofan injection material injected through openings formed in the tie. Theinjection material has a viscosity below 30 poise at a temperature nothigher than 200.degree. C. before hardening, and when hardened it has acompressive stress at 10% strain of 0.4 to 30 kg/cm.sup.2 at acompressive strain rate at 40.degree. C. of 1.5% per minute. The blendmaterial may include asphalt and a low molecular weight polypropylenehaving a molecular weight of 500-8000 or a high molecular weightpolypropylene having a molecular weight of 10,000-100,000.

U.S. Pat. No. 5,952,412 to Greenberg, et al., issued Sep. 14, 1999 forpelletized rubber, discloses rubber pellets made of an amount ofvulcanized rubber and an amount of binder, with the vulcanized rubberpreferably being discarded rubber. Additionally discloses that therubber pellets will preferably contain an amount of filler materialswhich are plastic or rubber or combinations thereof so that thepreferred rubber pellet contains an amount of rubber equal to betweenabout 50% and about 95% by weight of the rubber pellet, an amount offiller material equal to between about 0 and about 45% by weight of therubber pellet, and an amount of binder equal to between about 5% andabout 10% by weight of the rubber pellet. Further discloses that therubber pellets are used in the formation of asphalt and are desirablebecause they provide necessary constituents to the asphalt and allow forelimination of equipment and separate ingredient addition steps from theasphalt formation process. Further discloses the invention is alsodesirable because it provides for a way to desirably dispose of wasterubber materials.

U.S. Patent Application Publication No. 20020042477, published Apr. 11,2002, to Jelling, discloses polymers which have been functionalized soas to be able to chemically react with polyamines to form adductscontaining at least one or more groups consisting of amino, amido,imino, imido, or imidazloyl. Furthermore, the invention teachesprocesses to prepare these adducts by solution, melt or in-situ methods.A further embodiment of the invention pertains to the use of polyolefinplastomers or elastomers, elastomeric polyethylene-polypropylene,compositions or interpolymers of styrenes olefins, which have beenchemically modified so that they react with polyamines to confer toasphalt significantly improved desired chemical and physical properties.

U.S. Pat. No. 6,444,731 to Memon, issued Sep. 3, 2002, discloses amethod for manufacturing modified asphalt characterized by adding adispersion agent such as furfural or vegetable oil to a modifiermaterial and then mixing the modifier material with asphalt. Furtherdiscloses that the dispersion agent facilitates dispersion of themodifier through the asphalt to form a homogeneous mixture. Furtherdiscloses that a first activator is added to the mixture to produce adevulcanized and stabilized asphalt material having improvedrheological, separation and solubility characteristics. Furtherdiscloses that a micro activator is also added to the mixture to improvethe ductility of the modified asphalt. Further discloses that themodifier material comprises granular crumb rubber or polymer.

U.S. Pat. No. 6,588,974 issued Jul. 8, 2003, and U.S. Pat. No. 6,913,416issued Jul. 5, 2005, both to Hildebrand, et al., disclose bitumen orasphalt for the production of road surfaces, road surfaces, and methodfor the preparation of bitumen or asphalt. The bitumen or asphaltcontains a proportion of paraffin obtained by Fischer-Tropsch synthesis(FT paraffin). Also disclosed are a road topping with the bitumen and amethod for producing a corresponding road topping or roadway coveringusing the bitumen.

U.S. Patent Application No. 20060223916, by Stuart Jr. et al., discloseset al. Oct. 5, 2006 a modified asphalt composition is providedcomprising at least one plastomer, at least one elastomer, and asphalt.More specifically, a modified asphalt composition is provided comprisingan oxidized polyethylene, a styrene-butadiene-styrene block copolymer,and asphalt. A hot mix asphalt composition is also provided comprisingthe modified asphalt composition and aggregate. Processes for producingthe modified asphalt composition and the hot mix asphalt composition isalso provided as well as articles produced from these inventivecompositions.

U.S. Patent Application Publication No. 20070218250, published Sep. 20,2007, to Kiik et al., discloses roofing material that consistsessentially of a substrate, a hot melt material applied to one side ofthe substrate, an asphalt material coating the other side of thesubstrate and roofing granules disposed on said asphalt material coatedon the substrate. The hot melt material may be polyethylene,polyethylene-vinyl acetate, polypropylene, polyvinylidene chloride,polyester, nylon and mixtures thereof. The asphalt material may includenon-asphaltic filler.

U.S. Patent Application Publication No. 20080153945, published Jun. 26,2008, to Prejean, discloses a polymer-modified asphalt compositioncomprising an elastomeric polymer blend, a low molecular weightplastomer which may be a polyolefin wax, and an unmodified asphalt.Asphalt compositions of the present invention demonstrate improvedelasticity and stiffness compared to conventional polymer-modifiedasphalt compositions.

U.S. Patent Application Publication No. 20090053405, published Feb. 26,2009, to Martin, discloses bituminous asphalt binder materials that aremodified by the addition of crumb rubber or ground tire rubber and across-linking agent are described. In addition, methods are provided forproducing a modified asphalt binder containing crumb rubber or groundtire rubber and a cross-linking agent. The modified asphalt binderscomprise neat asphalt, crumb rubber, one or more acids and across-linking agent. Optionally, the modified asphalt binder may includeone or more polymer additives, including, polyethylene (linear orcrosslinked) and polypropylene (atactic or isotactic). The crumb rubbermay be obtained from recycled truck and/or automobile tires. Theaddition of crumb rubber in asphalt binders can improve the consistencyand properties of the asphalt binders at high and low temperatures. Inparticular, the modified asphalt binders of the present inventionexhibit improved elastic behavior, resulting in improved performance ofroads or other surfaces paved using the modified asphalt binder. Roadresistance to permanent deformation, fatigue cracking and thermalcracking is improved by use of the modified asphalt binder.

U.S. Patent Application Publication No. 20090054562, published, Feb. 26,2009, to Martin, discloses in a first aspect, bituminous asphalt bindermaterials which are modified by the addition of crumb rubber or groundtire rubber are described, and discloses in a second aspect, the presentinvention is directed to methods of producing a modified asphalt bindercontaining crumb rubber or ground tire rubber. The modified asphaltbinders comprise neat asphalt, crumb rubber, one or more syntheticpolymers which may include polyethylene, and one or more acids. Thecrumb rubber may be obtained from recycled truck and/or automobiletires.

The stability of polymer modified asphalt is generally determined by theSeparation test (‘cigar tube test’) ASTM D 7173; Determining SeparationTendency of Polymer from Polymer Modified Asphalt. The closer thetemperature between the top and the bottom of the cigar tube, the higherthe stability. The guidelines as issued by the American Association ofState Highway and Transportation Officials (AASHTO) are utilized in manyasphalt road formulations. The AASHTO has standardized test designationsin the form of T ### for standard laboratory specifications. Forexample, the AASHTO Cigar Tube Test is T 53. SBS is regarded as the goldstandard benchmark for modifying asphalt, with SBS modified asphalthaving a cigar test of 2° C. (3.6° F.) temperature differential. Recentprice spikes and shortages of SBS have led to a search for otherpolymers as replacements for SBS in order to modify asphalt. However,while cheaper and/or more available replacement polymers can be found,the stability of the replacement polymers has generally beendisappointing. For example, ground tire rubber (GTR) modified asphaltwill have a cigar tube test result of 30° F. difference or worse. Somedepartments of transportation will allow a cigar test result as high as15° F., while others sometimes waive the 2° C. requirement entirely.However, future trends point to the enforcement of 2° C. (3.6° F.) cigartube standard, meaning that either SBS will have to be used, or asuitable replacement found.

All of the patents, publications, articles and/or materials cited inthis specification, are herein incorporated by reference.

However, in spite of the above advancements, there still exists a needin the art for asphalt compositions and products, and to methods ofmaking and using such compositions and products.

This and other needs in the art will become apparent to those of skillin the art upon review of this specification, including its drawings andclaims.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide asphalt compositionsand products, and to methods of making and using such compositions andproducts.

This and other objects of the present invention will become apparent tothose of skill in the art upon review of this specification, includingits drawings and claims.

According to one non-limiting embodiment of the present invention, thereis provided an asphalt comprising petroleum asphalt a polyolefincomponent and, a wax component.

According to another non-limiting embodiment of the present invention,there is provided a method of treating a petroleum asphalt, the methodcomprising, contacting a petroleum asphalt with a polyolefin componentand a wax component to form a treated asphalt.

According to even another non-limiting embodiment of the presentinvention, there is provided an asphalt additive comprising polyolefincomponent, and a wax component.

According to still another non-limiting embodiment of the presentinvention, there is provided an asphalt comprising a first componentcomprising a petroleum asphalt; a second component comprising particlescomprising a polyolefin and a binder; wherein the second component isdispersed within the first component.

According to yet another non-limiting embodiment of the presentinvention, there is provided a method of treating a petroleum asphalt,the method comprising, contacting a petroleum asphalt with particlescomprising a polyolefin component and a binder component to form atreated asphalt.

According to still another non-limiting embodiment of the presentinvention, there is provided a method of making an asphalt additivecomprising forming particles from a melted mixture comprising apolyolefin and a binder.

Various sub-embodiments of the above embodiments includesub-embodiments: wherein the polyolefin component comprises at least oneselected from the group of C2 to C36 polyolefin homo-polymers, blends oftwo or more such polymers, and copolymers of two or more such polymers,and the binder component may comprise a petroleum micro-wax derived fromcrude oil refining processes; wherein the polyolefin component comprisesa melting point range from 115° C. to 250° C.; wherein the polyolefincomponent comprises at least one selected from the group ofpolypropylene homo-polymers and ethylene/propylene copolymers, and thewax component comprises a petroleum micro-wax derived from crude oilrefining processes; wherein the wax component comprises a melting pointin the range of 150° F. (66° C.) to 220° F. (104° C.); and/or whereinthe binder component is selected from the group consisting of:Polyolefin waxes, Polyethylene By-Product Waxes, Fischer-Tropsch HardWax, SBS, SB, SEBS, SBR, Natural and Synthetic Latex, crumb Tire Rubberand Elvaloy Terpolymer, Trinidad Lake Asphalt (TLA), Gilsonite, MontanWaxes, tall oil and tall oil derived products (both solids and liquids),vegetable oils, synthetic and petroleum micro-crystalline waxes, andnatural Rubber. In some non-limiting embodiments, the binder comprises awax.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; and, a second component comprising particles formed from amelted mixture of a resin and a binder; wherein, the second component isdispersed within the first component; wherein the resin is selected fromthe group consisting of at least one polymer alpha olefin selected fromthe group consisting of polyethylene homopolymer, homopolymers formedfrom α-olefins having more than 3 carbon atoms, and copolymers formedfrom 2 or more different α-olefins having 2 or more carbon atoms; and,wherein the binder is selected from the group consisting of polyethyleneby-product waxes, petroleum micro waxes, Fischer-Tropsch hard wax,Trinidad Lake asphalt (TLA), gilsonite, terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided a method of treating a petroleum asphalt, the methodcomprising: contacting a petroleum asphalt with particles formed from amelted mixture of a resin component and a binder component to form atreated asphalt, wherein the resin is selected from the group consistingof at least one polymer alpha olefin selected from the group consistingof polyethylene homopolymer, homopolymers formed from α-olefins havingmore than 3 carbon atoms, and copolymers formed from 2 or more differentα-olefins having 2 or more carbon atoms; and, wherein the binder isselected from the group consisting of polyethylene by-product waxes,petroleum micro waxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt(TLA), gilsonite, terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; a second component dispersed in the asphalt comprisingparticles formed from a melted mixture of a resin and a binder; and, athird component dispersed in the asphalt selected from the groupconsisting of ground tire rubber and polymers of styrene and butadiene,wherein the resin is selected from the group consisting of at least onepolymer alpha olefin selected from the group consisting of polyethylenehomopolymer, homopolymers formed from α-olefins having more than 3carbon atoms, and copolymers formed from 2 or more different α-olefinshaving 2 or more carbon atoms; and, wherein the binder is selected fromthe group consisting of polyethylene by-product waxes, petroleum microwaxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt (TLA), gilsonite,terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided a method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with a first component and asecond component, wherein the first component comprises particles formedfrom a melted mixture of a resin and a binder; and, the second componentis selected from the group consisting of ground tire rubber and polymersof styrene and butadiene, wherein the resin is selected from the groupconsisting of at least one polymer alpha olefin selected from the groupconsisting of polyethylene homopolymer, homopolymers formed fromα-olefins having more than 3 carbon atoms, and copolymers formed from 2or more different α-olefins having 2 or more carbon atoms; and, whereinthe binder is selected from the group consisting of polyethyleneby-product waxes, petroleum micro waxes, Fischer-Tropsch hard wax,Trinidad Lake asphalt (TLA), gilsonite, terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; and, a second component comprising particles formed from amelted mixture of a resin and a binder; wherein, the second component isdispersed within the first component; wherein the resin is selected fromthe group consisting ethylene vinyl acetate; polystyrene; styrenebutadiene block copolymer; styrene ethylene butylene styrene; naturalrubber, synthetic rubber; styrene-butadiene rubbers; and, wherein thebinder is selected from the group consisting of polyethylene by-productwaxes, petroleum micro waxes, Fischer-Tropsch hard wax, Trinidad Lakeasphalt (TLA), gilsonite, terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided a method of treating a petroleum asphalt, the methodcomprising: contacting a petroleum asphalt with particles formed from amelted mixture of a resin component and a binder component to form atreated asphalt, wherein the resin is selected from the group consistingethylene vinyl acetate; polystyrene; styrene butadiene block copolymer;styrene ethylene butylene styrene; natural rubber, synthetic rubber;styrene-butadiene rubbers; and, wherein the binder is selected from thegroup consisting of polyethylene by-product waxes, petroleum microwaxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt (TLA), gilsonite,terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; a second component dispersed in the asphalt comprisingparticles formed from a melted mixture of a resin and a binder; and, athird component dispersed in the asphalt selected from the groupconsisting of ground tire rubber and polymers of styrene and butadiene,wherein the resin is selected from the group consisting of ethylenevinyl acetate; polystyrene; styrene butadiene block copolymer; styreneethylene butylene styrene; natural rubber, synthetic rubber;styrene-butadiene rubbers; and, wherein the binder is selected from thegroup consisting of polyethylene by-product waxes, petroleum microwaxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt (TLA), gilsonite,terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided a method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with a first component and asecond component, wherein the first component comprises particles formedfrom a melted mixture of a resin and a binder; and, the second componentis selected from the group consisting of ground tire rubber and polymersof styrene and butadiene, wherein the resin is selected from the groupconsisting of ethylene vinyl acetate; polystyrene; styrene butadieneblock copolymer; styrene ethylene butylene styrene; natural rubber,synthetic rubber; styrene-butadiene rubbers; and, wherein the binder isselected from the group consisting of polyethylene by-product waxes,petroleum micro waxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt(TLA), gilsonite, terpolymer, and montan waxes.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; and, a second component comprising particles formed from amelted mixture of a resin and a binder; wherein, the second component isdispersed within the first component; wherein the resin is selected fromthe group consisting of reactive elastomeric terpolymers, polymershaving glycidyl functionality, polymers having glycidyl acrylatefunctionality, and polymers having epoxide functionality; and, whereinthe binder is selected from the group consisting of polyethyleneby-product waxes, petroleum micro waxes, Fischer-Tropsch hard wax,Trinidad Lake asphalt (TLA), gilsonite, and montan waxes.

According to another non-limiting of the present invention, there isprovided a method of treating a petroleum asphalt, the methodcomprising: Contacting a petroleum asphalt with particles formed from amelted mixture of a resin component and a binder component to form atreated asphalt, wherein the resin is selected from the group consistingof reactive elastomeric terpolymers, polymers having glycidylfunctionality, polymers having glycidyl acrylate functionality, andpolymers having epoxide functionality; and, wherein the binder isselected from the group consisting of polyethylene by-product waxes,petroleum micro waxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt(TLA), gilsonite, and montan waxes.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; a second component dispersed in the asphalt comprisingparticles formed from a melted mixture of a resin and a binder; and, athird component dispersed in the asphalt selected from the groupconsisting of ground tire rubber and polymers of styrene and butadiene,wherein the resin is selected from the group consisting reactiveelastomeric terpolymers, polymers having glycidyl functionality,polymers having glycidyl acrylate functionality, and polymers havingepoxide functionality; and, wherein the binder is selected from thegroup consisting of polyethylene by-product waxes, petroleum microwaxes, Fischer-Tropsch hard wax, Trinidad Lake asphalt (TLA), gilsonite,and montan waxes.

According to another non-limiting of the present invention, there isprovided a method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with a first component and asecond component to form a modified asphalt, wherein the first componentcomprises particles formed from a melted mixture of a resin and abinder; and, the second component is selected from the group consistingof ground tire rubber and polymers of styrene and butadiene, wherein theresin is selected from the group consisting of reactive elastomericterpolymers, polymers having glycidyl functionality, polymers havingglycidyl acrylate functionality, and polymers having epoxidefunctionality; and, wherein the binder is selected from the groupconsisting of polyethylene by-product waxes, petroleum micro waxes,Fischer-Tropsch hard wax, Trinidad Lake asphalt (TLA), gilsonite, andmontan waxes.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; and, a second component comprising particles formed from amelted mixture of a resin and a binder; wherein, the second component isdispersed within the first component; wherein the resin is polypropylenehomopolymer; and, wherein the binder comprises a terpolymer comprisingat least one of glycidyl functionality, glycidyl acrylate functionality,or epoxide functionality.

According to another non-limiting of the present invention, there isprovided a method of treating a petroleum asphalt, the methodcomprising: contacting a petroleum asphalt with particles formed from amelted mixture of a resin component and a binder component to form atreated asphalt, wherein the resin is polypropylene homopolymer; and,wherein the binder comprises a terpolymer comprising at least one ofglycidyl functionality, glycidyl acrylate functionality, or epoxidefunctionality.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; a second component comprising particles formed from a meltedmixture of a resin and a binder; and, a third component dispersed in theasphalt selected from the group consisting of ground tire rubber andpolymers of styrene and butadiene, wherein the resin is polypropylenehomopolymer; and, wherein the binder comprises a terpolymer comprisingat least one of glycidyl functionality, glycidyl acrylate functionality,or epoxide functionality.

According to another non-limiting of the present invention, there isprovided a method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with a first component and asecond component, wherein the first component comprises particles formedfrom a melted mixture of a resin and a binder; and, the second componentis selected from the group consisting of ground tire rubber and polymersof styrene and butadiene, wherein the resin is polypropylenehomopolymer; and, wherein the binder comprises a terpolymer comprisingat least one of glycidyl functionality, glycidyl acrylate functionality,or epoxide functionality.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; and, a second component comprising particles of resin; whereinthe resin is selected from the group consisting of polyalphaolefins,ethylene vinyl acetate, polystyrene, styrene butadiene block copolymer,styrene ethylene butylene styrene, natural rubber, synthetic rubber,styrene-butadiene rubbers, reactive elastomeric terpolymers, polymershaving glycidyl functionality, polymers having glycidyl acrylatefunctionality, and polymers having epoxide functionality; and the resinparticles have a diameter less than about 420 microns.

According to another non-limiting of the present invention, there isprovided a method of treating a petroleum asphalt, the methodcomprising: contacting a petroleum asphalt with particles of resincomponent, wherein the resin is selected from the group consisting ofpolyalphaolefins, ethylene vinyl acetate, polystyrene, styrene butadieneblock copolymer, styrene ethylene butylene styrene, natural rubber,synthetic rubber, styrene-butadiene rubbers, reactive elastomericterpolymers, polymers having glycidyl functionality, polymers havingglycidyl acrylate functionality, and polymers having epoxidefunctionality; and the resin particles have a diameter less than about420 microns.

According to another non-limiting of the present invention, there isprovided an asphalt comprising: a first component comprising a petroleumasphalt; a second component dispersed in the asphalt comprising resinparticles; and, a third component dispersed in the asphalt selected fromthe group consisting of ground tire rubber and polymers of styrene andbutadiene, wherein the resin is selected from the group consisting ofpolyalphaolefins, ethylene vinyl acetate, polystyrene, styrene butadieneblock copolymer, styrene ethylene butylene styrene, natural rubber,synthetic rubber, styrene-butadiene rubbers, reactive elastomericterpolymers, polymers having glycidyl functionality, polymers havingglycidyl acrylate functionality, and polymers having epoxidefunctionality; and the resin particles have a diameter less than about420 microns.

According to another non-limiting of the present invention, there isprovided a method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with a first component and asecond component to form a modified asphalt, wherein the first componentcomprises resin particles; and, the second component is selected fromthe group consisting of ground tire rubber and polymers of styrene andbutadiene, wherein the resin is selected from the group consisting ofpolyalphaolefins, ethylene vinyl acetate, polystyrene, styrene butadieneblock copolymer, styrene ethylene butylene styrene, natural rubber,synthetic rubber, styrene-butadiene rubbers, reactive elastomericterpolymers, polymers having glycidyl functionality, polymers havingglycidyl acrylate functionality, and polymers having epoxidefunctionality; and the resin particles have a diameter less than about420 microns.

According to another non-limiting of the present invention, there isprovided a method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with an additive to form amodified asphalt, wherein the additive comprises ground tire rubber andresin, wherein the resin is selected from the group consisting ofreactive elastomeric terpolymers, polymers having glycidylfunctionality, polymers having glycidyl acrylate functionality, andpolymers having epoxide functionality.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is TABLE 7, Separation Test Results for Test Highway usingRheopave 10XP.

FIG. 2 is TABLE 9, PG67-22 Base Asphalt Upgraded to PG76-22 GTR withMSCR Specification.

FIG. 3 is TABLE 11 for PG (ARB)-22 Test Sections.

FIGS. 4A and 4B are TABLE 12, Part 1 and TABLE 12, Part 2, respectively,showing certification for the Rheopave modified asphalt.

FIGS. 5A and 5B are TABLE 13, Part 1 and TABLE 13, Part 2, respectively,showing certification for the Rheopave modified asphalt.

DETAILED DESCRIPTION OF THE INVENTION

This invention describes an additive used as an asphalt binder modifierthat in some embodiments includes a polymer component that is theprimary rheology modifying component, and a secondary rheology modifyingcomponent. In some non-limiting embodiments of the present invention,the primary rheology modifying component and the secondary rheologymodifying component are melted together into a single liquid phasebefore being formed into a solid asphalt additive. In other non-limitingembodiments, the additive comprises only the primary rheology modifyingcomponent(s). This invention may find applicability with any type ofasphalt including straight asphalt and blown asphalt. As a moreparticular non-limiting example, this invention finds applicability inpaving applications with straight asphalt. As non-limiting examples, theadditive may be in some sort of solid form, non-limiting examples ofwhich include a one pack additive in pastille, bead, pill or granuleform. In some non-limiting embodiments, the additive provides forPavement and Roofing applications that meet the target PerformanceGrading (PG) in terms of binder stiffness (as measured by the DynamicShear Rheometer or Softening Point) and Low Temperature flexibility (asmeasured by Bending Beam Rheometer or Fraas Breaking point or MandrelBending Test). Further, this invention may be formulated by specificdesign to produce the desired binder within the “Warm Mix Asphalt”concept for Paving applications as well as reduced temperature andenhanced application speeds for Roofing applications. In othernon-limiting embodiments, the additive of the present inventionfunctions to stabilize ground tire rubber in asphalt as measured by thecigar tube test.

Some embodiments of the present invention may also find use in providingroofing and paving materials having improved UV resistance.

Some non-limiting methods of the present invention may obviate the needfor grinding of polymers at the point of mixing with bitumen.

Some non-limiting embodiments of the present invention may facilitatethe addition of crumb rubber to asphalt.

Some non-limiting embodiments of the present invention may prevent orreduce phasing of crumb rubber in asphalt formulations.

In some embodiments, the combined effect of the additive package may beto reduce the asphalt aggregate mixing, transportation, lay down and/orcompaction temperatures, by between 10° C. (50° F.) to 32° C. (90° F.)as a non-limiting example. Further, in certain embodiments, thisinvention may provide the benefit of enhancing the useful temperaturerange of the modified asphalt binder. This additive may be used tomodify the asphalt binder first and then add to the aggregate mix or itmay be added directly to the aggregate mixing drum whether a continuousdrum mixer or a batch mixer. Some embodiments provide ease oftransportation, storage and handling.

The present invention utilizes one or more polymers as the primaryrheology modifying component. In some non-limiting embodiments, thisprimary rheology modifying component may be a polyolefin homo-polymer orcopolymer resins. In some non-limiting embodiments, the polyolefinhomopolymer or copolymer is a poly α-olefin (“PAO”), which may be formedfrom polymerizing same (in the case homopolymer) or 2 or more different(in the case of copolymer) C2 to C36 α-olefins (i.e. α-olefins havingfrom 2 to 36 carbon atoms). The PAO copolymers may be formed by mixing 2or more already formed PAO's, by copolymerizing 2 or more differentPAO's, by copolymerizing 2 or more different α-olefins, or anycombination of the foregoing. In non-limiting examples, these polyolefinresins may include polyethylene (“PE”) homopolymers, polypropylene(“PP”) homo-polymer and polypropylene/polyethylene (“PP/PE”) co-polymerresins and by-product waxes in asphalt modification. Since these resinshave a substantially higher melting point (above 140° C.) than the baseasphalt binder (approximately 60° C.), the use of such resins has beenexcluded since the asphalt binder would degrade and become a fumeemission hazard at such high temperatures. The technology describedherein is novel in producing a compound of certain polymers, as anon-limiting example the PE homo-polymer, PP Homo-polymer and/or PP plusPE co-polymer, such that the compound is uniquely dispersible in asphaltbinder at the safe and usual operating temperatures. In somenon-limiting embodiments, the resin is combined with a binder (in someembodiments melted together). Without being limited by theory,applicants believe that when the particles of polyolefin resin/binder(or in general the primary rheology modifying component) are heated tothe melt point of the binder (or in general the secondary rheologymodifying component), the binder materials quickly melt and physicallypartition the resin molecules such that the resin will fall apart in thehot/warm asphalt base and disperse quickly and homogenously. In this waythe additive value in certain embodiments may be realized to “bump” thehigh temperature PG to the desired level whilst at the same time takingthe Low temperature PG value to the desired grade i.e. the uniqueability to “stretch the PG box” or escalate the useful performancetemperature range of the asphalt binder.

A non-limiting example of suitable polyolefin materials includepolyethylene (PE) homo-polymer or polypropylene (PP) homo-polymer havinga molecular weight in the range of about 20,000 to about 200,000. Anon-limiting example of suitable PP plus polyethylene (PE) co-polymerincludes those having a molecular weight in the range of about 20,000 toabout 200,000.

A second aspect of this novel invention is that the systems describedherein meets the requirements of “Warm Mix Asphalt Paving”.

This invention describes an asphalt/bitumen additive formulation thatmay be used in combination with modified or unmodified asphalt binderand aggregates to produce an aggregate paving mixture used to paveroads/pavements. In some non-limiting embodiments, the primary rheologymodifying component comprises a polyolefin homo-polymer and/or copolymerin any ratio. Some non-limiting embodiments employ PE homo-polymerresin, PP Homo-polymer resin or PP plus PE co-polymer resin orcombinations of these in any ratio. As a non-limiting example, theresins described herein have a melting point range of 266° F. (130° C.)to 482° F. (250° C.) and above.

While the “primary rheology modifying component” (i.e., resin component)is mostly described herein in terms of polyolefins, the primary rheologycomponent should not be considered so limited, as there are otherpolymers that are believed to also be useful as the “primary rheologymodifying component” in the present invention, including, but notlimited to ethylene vinyl acetate; polystyrene; styrene butadiene blockcopolymer (SB); styrene ethylene butylene styrene (SEBS); naturalrubber, synthetic rubber (most commonly styrene-butadiene rubbers (SBR)derived from the copolymerization of styrene and 1,3-butadiene; but mayalso include synthetic rubbers are prepared from isoprene(2-methyl-1,3butadiene), chloroprene (2-chloro-1,3-butadiene), andisobutylene (methylpropene) with a small percentage of isoprene forcross-linking); reactive elastomeric terpolymers (RET) a non-limitingexample of which includes alkylene-alky acrylate-glycidyl acrylateterpolymers; polymers having glycidyl or glycidyl acrylate functionalitya non-limiting example of which includes alkylene-alkylacrylate-glycidylacrylate terpolymers, and polymers having an epoxide functionality. Anon-limiting example of a suitable alkylene-alklyacrylate-glycidylacrylate terpolymers includes ethylene-butyl acrylate-glycidylmethacrylate tepolymers, a commercial example of which are Elvaloy®terpolymers.

In some embodiments, the primary rheology modifying component willcomprise at least one PAO selected from the group consisting ofhomopolymers and copolymers formed from α-olefins having 2 or morecarbon atoms.

In some embodiments, the primary rheology modifying component willcomprise at least one selected from the group consisting of polyethylenehomopolymer, homopolymers formed from α-olefins having more then 3carbon atoms, and copolymers formed from 2 or more different α-olefinshaving 2 or more carbon atoms.

As a non-limiting example, certain embodiments of the present inventionutilize as the primary rheology modifying component, a reactiveelastomeric terpolymer which in some embodiments may be in combinationwith polystyrene, styrene butadiene block copolymer (SB), styreneethylene butylene styrene (SEBS), and styrene-butadiene rubbers (SBR).

As another non-limiting example, certain embodiments of the presentinvention utilize as the primary rheology modifying component polymershaving glycidyl methacrylate functionality which in some embodiments maybe in combination with polystyrene, styrene butadiene block copolymer(SB), styrene ethylene butylene styrene (SEBS), and styrene-butadienerubbers (SBR).

Polymers with epoxide functionality, include those derived frombisphenols, non-limiting examples of which include bisphenol A,bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C,bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S,bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z.

Some embodiments of the present invention provide the use of a secondaryrheology modifying component having a lower melting point than theprimary rheology modifying component, that when the additive issubjected to the hot/warm asphalt base, the secondary rheology modifyingcomponent(s) quickly melts and physically partitions the primaryrheology modifying component(s) such that the primary rheology modifyingcomponent(s) will fall apart in the hot/warm asphalt base and dispersequickly and homogenously. The main requirement of the secondary rheologymodifying component is that it have a lower melting point that theprimary rheology modifying component, and will quickly melt when theadditive is introduced to the hot/warm asphalt. The quicker that thesecondary rheology modifying component can melt than the primaryrheology modifying component when the additive is exposed to thehot/warm asphalt base, the better. It is believed that a wide range ofpolymers may function as the secondary rheology modifying component.

As non-limiting examples, some embodiments may employ a secondaryrheology modifying component which may comprise a petroleum micro-waxobtained from conventional crude refining. This secondary rheologymodifying component, or binder for the primary rheology modifyingcomponent, may act as a partitioning/dispersion agent for the primaryrheology modifying component, and can be any one of waxes, vegetableoils and most hydrocarbons in the melt point range of 70 C to 135 C.

This secondary rheology modifying component may be referred to herein asa binder, dispersant, or binding, dispersing or partitioning agent. As anon-limiting example, a suitable wax may have a melting point rangebetween 140° F. (60° C.) to 239° F. (115° C.). In some non-limitingembodiments, it may be at times be desired to use a blend of two or moreseparate micro-waxes in the above melt range to achieve the desiredrheology properties. The dispersing effect may also be achieved throughthe use of an additional component that is either Crude Tall Oil (CTO)or an oxidized Tall Oil Pitch. Non-limiting examples of other secondaryrheology modifiers that may be used alone or in any combination may beLow Molecular Weight PE Waxes, Fischer-Tropsch Waxes, Petroleum ParaffinWaxes, Montan Wax, SBS, SBR, Natural and Synthetic Latex, Trinidad LakeAsphalt, Gilsonite and other natural asphalts, Crumbed Tire Rubber, etc.As a non-limiting example a polyethylene (“PE”) wax having a molecularweight in the range of about 650-2500, although a PE wax having amolecular weight greater or less than that range may also be suitable.As another non-limiting example, a Fischer-Tropsch wax having amolecular weight in the range of about 450-1200, although aFischer-Tropsche wax having a molecular weight greater or less than thatrange may also be suitable. Another non-limiting example of suitablesecondary rheology modifying components includes reactive elastomericterpolymers (RET) a non-limiting example of which includes alkylene-alkyacrylate-glycidyl acrylate terpolymers; polymers having glycidyl orglycidyl acrylate functionality a non-limiting example of which includesalkylene-alkylacrylate-glycidyl acrylate terpolymers, and polymershaving an epoxide functionality. A non-limiting example of a suitablealkylene-alklyacrylate-glycidyl acrylate terpolymers includesethylene-butyl acrylate-glycidyl methacrylate tepolymers, a commercialexample of which are Elvaloy® terpolymers.

The additive package described above may contribute to the Warm Mix inthe following manner:

(a) In some non-limiting embodiments, the reduction in viscosity of theasphalt binder may be achieved through the combination ofrheology/viscosity modifiers described above, that in turn reduces theviscosity of the aggregate mix making it possible to compact the mix atthe lower temperatures in the Warm Mix range.

(b) In some non-limiting embodiments, the CTO and or oxidized tall oilpitch acts as a dispersing agent for the primary rheology modifyingcomponent, (as a non-limiting example, polyolefin homo-polymer andco-polymer resins), and may further reduce the viscosity of the additivepackage thereby contributing to further improvements in compaction andincreasing the useful paving window.

(c) In some non-limiting embodiments, the combination of the primaryrheology modifying component (as a non-limiting example polyolefinhomo-polymer and co-polymer resins) may contribute to the binderstiffness at the pavement performance temperature producing the effectof a performance grading grade bump.

(d) In some non-limiting embodiments, the combination of micro-waxesprovides the effect of viscosity reduction at the paving temperatureswhile contributing to the binder and pavement flexibility at LowTemperatures during winter periods. In this way the stiffness of thebinder may be offset at Low Temperature Performance.

(e) In some non-limiting embodiments, the CTO and oxidized CTO mayperform as adhesive agents linking the asphalt binder to the aggregatesurfaces.

Different combinations of the secondary rheology modification componentmay be used to achieve the specific desired specification/property suchthat several grades of the additive may be commercially produced.

The additive invention described above can easily be used in anyconvential Hot Mix asphalt to reduce the asphalt mix production,transportation, paving and compaction temperatures. As a non-limitingexamples, to reduce temperatures by between 10° C. (50° F.) to 32° C.(90° F.). The additive package may be first added to the asphalt binderand the so modified binder may be added to the aggregate mix in acontinuous drum mixer or batch mixer. Also, the additive package may beadded directly to the aggregate mix in a continuous drum mixer or abatch mixer immediately after the binder comes into contact with theaggregate.

The additive package may also be used for surface dressings such as hotapplied chip seals, slurry seals and such surface dressings as aviscosity reducer and to eliminate the use of volatile cut back solventsand associated fume emissions. Such Warm Mix applications may alsoinclude coatings and sealants for moisture protection as well as solventand chemical resistance mixtures.

The additive package described herein may also be used in Roofingapplications as follows:

(1) In a non-limiting example for the manufacture of roofing shingles,the asphalt binder may be modified with the described additive packageto meet the target specifications (Softening Point, Penetration, FlashPoint, Ductility, Tensile Strength, and/or UV resistance, etc.) and maythen be coated onto the non-woven substrate (usually glass fiber).

(2) In a non-limiting example for the manufacture of Built Up Roofing(BUR) grades or Mopping Grades, the additive package described hereinmay be used to modify the asphalt binder to achieve the desiredspecifications (Softening Point, Penetration, Flash point, Ductility,Tensile Strength, etc.) and then used for Hot Applied or EmulsionApplied coatings.

(3) In a non-limiting example, the additive package may be used tomanufacture adhesive coatings for roofing applications.

(4) In a non-limiting example, the additive package described herein maybe used in asphalt feed stocks prior to blowing to harden the binderthrough oxidation. As a non-limiting example the additive package willbe present in the at 0.5% up to 10% range by weight, although more than10% and less than 0.5% are also believed to be beneficial. The benefitsof this additive are reduced batch cycle times for example by 20% to35%, less aging of the blown binder, lower viscosity and workability ofthe blown binder and easier achievement of target specifications. Also,this technology may enable the blowing methods to operate on a wideravailable pool of asphalts including fluxes and paving grades to achievethe same target specifications. In some embodiments in which the blowingoperation can actually be operated at lower blowing temperatures, awider pool of asphalts may become available for blowing.

The polyolefin homo-polymer and copolymer utilized herein may beobtained by any suitable method and means, using any suitable catalystas is well known in the polyolefin art. As a non-limiting example,suitable polyolefin may be derived from olefins having from about 2 toabout 36 carbon atoms, or may comprise blends of two or more of suchpolyolefins, or may comprises copolymers of two or more such olefins. Asa non-limiting example, PP homo-polymer and PP plus PE co-polymer may bederived from the manufacture of PP resins either as a by-productstream(s) or as intermediate grades during the changeover form one gradeto the next. These streams may be collected from the process andsegregated into several qualities and which may be combined again toyield product that is suitable for specific asphalt applications eitheras such or in combination with the secondary rheology modifying agentdescribed herein.

As a non-limiting embodiment, when manufactured as a compound, the resinor by-product wax content of the additive package may comprise in therange of 5% to 95% and preferably in the range of 50% to 85%. TheMelting Point of the resin or by-product wax component is in the rangeof 120 C (248 F) to 200 C (392 F) and preferably in the range of 130 C(266 F) to 175 C (347 F).

In some non-limiting embodiment, the resin component may comprise aNeedle Penetration at 77° F. in the range of 0 to 10 (units being 0.1mm).

The resin component or primary rheology portion serves as a onecomponent of the rheology/viscosity modifier and may also contribute tothe overall binder stiffness at the pavement performance temperature asmeasured by the Dynamic Shear Rheometer.

Any suitable petroleum wax may be utilized in the present invention asdesired. As a non-limiting example, the petroleum micro-wax may bederived from crude oil refining processes. One non-limiting example of asuitable petroleum was has a melting point in the range of 150° F. (66°C.) to 220° F. (104° C.). A combination of two or more separatemicro-wax streams may also be used at times to achieve the desiredeffect. In some embodiments, the micro-wax may serve a dual purpose ofviscosity modifier as well as to impart Low Temperature Performanceflexibility to the asphalt binder and pavement mix.

The content of micro-wax in the additive package can be in the range offrom 2, 5, 10, 15, 20, 30, 40, 50 60, 70 80 wt % to 50, 60, 70, 80, 90,95, and 99 wt %. As non-limiting examples in the range of about 2 to 50wt %, and in the range of 10 to 20 wt %.

In general, microcrystalline waxes are a type of wax produced byde-oiling petrolatum, as part of the petroleum refining process. Incontrast to the more familiar paraffin wax which contains mostlyunbranched alkanes, microcrystalline wax contains a higher percentage ofisoparaffinic (branched) hydrocarbons and naphthenic hydrocarbons. It ischaracterized by the fineness of its crystals in contrast to the largercrystal of paraffin wax. It consists of high molecular weight saturatedaliphatic hydrocarbons. It is generally darker, more viscous, denser,tackier and more elastic than paraffin waxes, and has a higher molecularweight and melting point. The elastic and adhesive characteristics ofmicrocrystalline waxes are related to the non-straight chain componentswhich they contain. Typical microcrystalline wax crystal structure issmall and thin, making them more flexible than paraffin wax.

Microcrystalline waxes when produced by wax refiners are typicallyproduced to meet a number of ASTM specifications. These include congealpoint (ASTM D938), needle penetration (D1321), color (ASTM D6045), andviscosity (ASTM D445). Microcrystalline waxes can generally be put intotwo categories: “laminating” grades and “hardening” grades. Thelaminating grades typically have a melt point of 140-175 F and needlepenetration of 25 or above. The hardening grades will range from about175-200 F, and have a needle penetration of 25 or below. Color in bothgrades can range from brown to white, depending on the degree ofprocessing done at the refinery level.

Microcrystalline waxes are derived from the refining of the heavydistillates from lubricant oil production. This by product then must bede-oiled at a wax refinery. The product then may have its odor removedand color removed (which typically starts as a brown or dark yellow).This is usually done by means of a filtration method or byhydro-treating the wax material.

A non-limiting example of a suitable crude oil derived micro-wax mayhave the following properties: Drop Melt Point (ASTM D 127) in the rangeof 150° F. (66° C.) to 220° F. (104° C.); and Kinematic Viscosity (ASTMD445) at 212° F. (100° C.) in the range 10 to 320 centi-stokes.

Any suitable Crude Tall Oil and Oxidized Tall Oil Pitch Component may beutilized in the present invention. As a non-limiting example, the crudetall oil and oxidized tall oil pitch component can be in the range of 2%to 20% of the formulation and preferably in the range of 2% to 10% ofthe formulation. The function of the oxidized tall oil pitch is as adispersant for the resins so that it is evenly distributed in the finalasphalt mixture to impart a consistent stiffness modulus to the asphaltbinder as well as to the asphalt mix.

As used herein, including the claims, “tall oil materials” includes manmade and naturally occurring tall oil, tall oil pitch, tall oil blends,and similar tall oil products. Tall oil is a liquid resinous materialthat may be obtained in the digestion of wood pulp from papermanufacture. Commercial tall oils comprise a complex of fatty acids,resin acids, sterols, higher alcohols, waxes and hydrocarbons. The acidcomponents also may be present as the esters thereof.

A common source of tall oil that may be used in the practice of thepresent invention is from pine trees. Besides cellulose, tall oilcontains fatty acids, esters, rosin acids, sterols, terpenes,carbohydrates and lignin. These may be separated when wood is convertedto paper pulp by the sulfide or Kraft process. The acids may then beneutralized in an alkaline digestion liquor. The mixture of rosin andfatty acid soap may be recovered by subsequent acidification thatreleases free rosin and fatty acids, the major constituents of tall oil.

A non-limiting example of a suitable oxidized tall oil pitch may havethe following properties: Softening Point in the range of 125° F. (52°C.) to 220° F. (104° C.); and Needle Penetration value at 25° C. in therange of 2 to 40 and preferably in the range of 5 to 20.

Some embodiments of the additive package of the present inventiondescribed herein may provide one or more of the following advantagesover other Warm Mix products:

(a) Some non-limiting embodiments may be in the form of a one packproduct that can be easily transported globally and handled to be addedeither to the asphalt binder and then to the aggregate mix as modifiedbinder or it may be added directly to the aggregate mixing drum.

(b) In some non-limiting embodiments, the aggregate particles may beevenly coated with binder due to the lower surface tension imparted bythe additive package to the binder. Also, the aggregate coated binder isnot as sticky as conventionally mixed aggregate and this influences theworkability of the aggregate mix and makes to less sticky ontotransportation and paving equipment. Also, the compacted pavement maysupport traffic quickly without having any issues of stickiness ontotraffic wheels.

(c) In some non-limiting embodiments, the high temperature PG (ie. thestiffness modulus) of the additive modified binder may be improvedwithout or with little degrading of the Low Temperature PG.

(d) In some non-limiting embodiments, the additive may be detected andquantified in binder samples or aggregate mix samples or field coresamples at any time during the life of the pavement and this is unlikemost Warm Mix technologies that merely dissipate and can no longer bedetected with passage of time.

Some embodiments of the present invention may incorporate one or moreother Rheology Modifying Components. Non-limiting examples of suchcomponents may be as follows.

1. Polyethylene By-Product Waxes (“polyethylene waxes” or “PE waxes”) inthe melt Point range of 100 C to 160 C. The content of the by-product PEwax can be in the range of 5% to 50% and preferably 5% to 20%. Thepurpose of the by-product PE wax is as a dispersant for the resincomponent as well as viscosity modifier.

2. Fischer-Tropsch Hard Wax in the melting point range of 70 C to 115 Cin the same content as described in (1) above.

3. SBS (styrene butadiene styrene), SB (styrene butadiene), SEBS(styrene ethylene butadiene styrene), SBR (styrene butadiene rubber),Natural and Synthetic Latex, Crumb Tire Rubber and a polymer havingglycidyl acrylate functionality, as a non-limiting example, ElvaloyTerpolymer, in the same content as described in (1) above. Elvaolyterpolymer is a commercially available ethylene-butyl acrylate(BA)-glycidyl methacrylate (GMA) terpolymer from DuPont, and may havecompositions such as 28 wt % BA and 5.3 wt % GMA or 20 wt % BA and 9 wt% GMA (the balance being ethylene in both).

4. Trinidad Lake Asphalt (TLA), Gilsonite, Montan Waxes and naturalRubber in the same content as described in (1) above.

5. Petroleum micro waxes as described above.

A non-limiting example of the present invention includes firstcontacting the polymeric primary rheology modifying component and thedispersant secondary rheology modifying component together prior toadding either to the asphalt. As a non-limiting example, the polymer andthe dispersant may both be melted and then thoroughly mixed togetherbefore being reformed into particles which may then be added to theasphalt. The melting may be accomplished separately with the meltedmaterials then added together, or may be accomplished separately butsimultaneously with the melted materials then added together, or may beaccomplished simultaneously with the unmelted materials contactedtogether and then melted, or may be accomplished sequentially with themelted materials then added together, or may be accomplished by firstmelting one than contacting it with the unmelted one and then furthermelting of both. As another non-limiting example, polymer particles maybe mixed into the melted dispersant with this mixture then formed intoparticles which may then be added to the asphalt. As even anothernon-limiting example, a dry mix of polymer particles and dispersantparticles may first be formed, and this mix added directly to theasphalt, or the dry mix may then be melted and formed into particleswhich may then be added to the asphalt. As a further non-limitingexample, the invention may also include use of a cross-linkingpre-cursor is incorporated into the mixture to initiate active sites onthe PP molecule chain and create a network structure in asphalt to giveunique stiffness modulus properties, separation, stability and UV lightprotection. In the practice of the present invention, selected additivesare chosen that are effective dispersing agents that partition betweenthe PP molecules and thereby cause the PP to fall apart and disperse inasphalt binders. The polymer and dispersant may be formed into particlesutilizing any suitable method/apparatus, including extrusion andsubsequent cutting, pelletizing and the like. As a non-limitingembodiment, pellets may be formed from a mixture of a polyolefin and awax (or in general from the primary rheology modifying component(s) andsecondary rheology modifying component(s)). A melted mixture may beformed by melting the polyolefin and wax together in any desired order(i.e., sequentially melting one and then melting the other and thenmixing, sequentially melting one and then mixing with the other unmeltedand then melting the mixture, simultaneously apart and then mixing,simultaneously together, or any other suitable order/arrangement). Asolid form of the additive, non-limiting examples of which includeparticles, pellets, pills, powder, pastilles, beads, granules, or thelike may be formed by any suitable method with any suitable apparatusincluding extrusion, pelletizing, cutting, chopping and the like.

In even another non-limiting embodiment pellets may be formed from amixture of a polyethylene homopolymer, polypropylene homopolymer orpolypropylene/polyethylene copolymer and a wax (or in general from theprimary rheology modifying component(s) and secondary rheology modifyingcomponent(s)). A melted mixture may be formed by melting the polymer andwax together in any desired order (i.e., sequentially melting one andthen melting the other and then mixing, sequentially melting one andthen mixing with the other unmelted and then melting the mixture,simultaneously apart and then mixing, simultaneously together, or anyother suitable order/arrangement). Particles, pellets, pills, powder,pastilles, beads, granules or the like may be formed by any suitablemethod with any suitable apparatus including extrusion, pelletizing,cutting, chopping and the like.

In still another non-limiting embodiment pellets may be formed from amixture of a polypropylene homopolymer or polypropylene/polyethylenecopolymer, and a polyethylene wax or a petroleum micro wax (or ingeneral from the primary rheology modifying component(s) and secondaryrheology modifying component(s)). A melted mixture may be formed bymelting the polymer and wax together in any desired order (i.e.,sequentially melting one and then melting the other and then mixing,sequentially melting one and then mixing with the other unmelted andthen melting the mixture, simultaneously apart and then mixing,simultaneously together, or any other suitable order/arrangement).Particles, pellets, pills, powder, pastilles, beads, granules or thelike may be formed by any suitable method with any suitable apparatusincluding extrusion, pelletizing, cutting, chopping and the like. Insome non-limiting embodiments the binder may comprise a polyethylenewax. In some non-limiting embodiments the binder may comprise apetroleum micro wax.

It is believed that any known asphalt composition or product may be madeusing the additives of the present invention to replace part or all ofthe petroleum based asphalt binder therein. Non-limiting examplesinclude blown asphalt and straight asphalt. As a non-limiting example, apaving application may be formed utilizing a straight asphalt. The knownequipment and methods of making the known asphalt compositions andproducts are believed to be sufficient for making the asphaltcompositions and products of the present invention in which part or allof the petroleum based asphalt has been partially or wholly replaced bymodified asphalt of the present invention.

In addition to the above embodiments, the present invention may alsoinclude the following non-limiting embodiments.

Non-limiting embodiments of the present invention include a one productadditive package formulation for asphalt modification which comprises PPhomo-polymer (or in general any of the primary rheology modifyingcomponent(s)) plus PE by-product wax and/or petroleum micro-wax and/orCTO and/or Oxidized Tall Oil Pitch and/or any of the Other RheologyModifying Agents above. In some embodiments, the additive may increasethe useful performance temperature range of the asphalt binder which mayalready be modified or not.

Non-limiting embodiments of the present invention include the additivepackage described above which may be used as the Warm Mix Asphalt Pavingconcept.

Non-limiting embodiments of the present invention include the additivepackage described above and which may be used in roofing applications.

Non-limiting embodiments of the present invention include the PE Waxdescribed above that is derived as a byproduct wax from polyethylenemanufacture in the Softening Point range of 215° F. (102° C.) to 275° F.(135° C.), Needle penetration value at 25° C. in the range of 2 to 10and Brookfield Viscosity at 300° F. in the range of 15 to 300 cps.

Non-limiting embodiments of the present invention include the PetroleumMicro-Wax described in the invention above that is derived from crudeoil refining and has a Drop Melt Point (ASTM D127) in the range of 150°F. (66° C.) to 220° F. (104° C.) and Kinematic Viscosity (ASTM D445) at212° F. (100° C.) in the range of 10 to 320 Centi-Stokes.

Non-limiting embodiments of the present invention include the oxidizedtall oil pitch described above with a Softening Point in the range of125° F. (52° C.) to 220° F. (104° C.).

Non-limiting embodiments of the present invention include the additivepackage described above used with neat asphalt binder or with polymermodified binder (including modified asphalt that has been modified withany of Styrene Butadiene Styrene, Styrene Butadiene Rubber, NaturalLatex Rubber, Synthetic Latex Rubber, Crumbed Tire Rubber, EthyleneVinyl Acetate, Terpolymers, and Atactic Polypropylene).

Non-limiting embodiments of the present invention include the additivepackage above used in roofing applications (including shingles, rolls,mop on grades, adhesives and sealants) to reduce working temperaturesand enhance workability.

Non-limiting embodiments of the present invention include the additivepackage described above used in hot applied surface dressings includingchip seals, slurry seals, joint sealants, crack sealants, etc.

Non-limiting embodiments of the present invention include a Warm Mixasphalt mix formulation for the pavement of road surfaces where theformulation comprises of a mixture of bitumen and aggregates and between0.2 to 30% by weight of the additive package based on weight of theasphalt binder content.

Non-limiting embodiments of the present invention include theformulation of above wherein the temperature of compaction of theaggregate mix is 10° F. to 90° F. below conventional Hot Mix asphalt.

Non-limiting embodiments of the present invention include the asphaltformulation above where the additive package may be added to the drummixer or batch mixer directly or added to the asphalt binder and thenintroduced into the drum mixer or batch mixer as additive modifiedbinder.

Non-limiting embodiments of the present invention include the Warm Mixasphalt of above wherein the additive package is added to produce a WarmMix aggregate, and also include embodiments wherein the individualcomponents of the additive package are added to produce the Warm Mixaggregate.

Non-limiting embodiments of the present invention include the additivepackage described above for use in co-extrusion with polymers and waxadditives to render these more easily dispersible in asphalt binders.These co-extrusion components may be any of the primary and/or secondaryrheology modifying components mentioned above.

Non-limiting embodiments of the present invention include the use of theany of the present invention for asphalt modification for Pavement andRoofing applications.

The additives of the present invention may be formed by a wide varietyof methods utilizing a wide variety of apparatus. All of the additivesherein may be utilized in combination with ground tire rubber (GTR) orany recycled rubber material. In some embodiments, it is necessary tostabilize the GTR in asphalt, which may be accomplished by the additionof the above described reactive elastomeric terpolymer, and/or with theabove described polymers having a glycidyl or glycidyl acrylatefunctionality, a non-limiting example of such functionality includesglycidyl methacrylate functionality, and a non-limiting example of sucha polymer includes ethylene-butyl acrylate-glycidyl methacrylateterpolymer (a commercial example of which is Elvaloy terpolymeravailable from DuPont). Further, it is believed that any of the polymersmentioned herein as suitable as the primary rheology modifying componentmay be functionalized with glycidyl or glycidyl acrylate (includingglycidyl methacryalate, and glycidyl ethacrylate functionality). In someembodiments, the secondary rheology modifying component is not necessaryto stabilize ground tire rubber in asphalt.

As explained above, the stability of GTR in asphalt is generallydetermined by the Separation test (‘cigar tube test’) ASTM D 7173;Determining Separation Tendency of Polymer from Polymer ModifiedAsphalt. The closer the temperature between the top and the bottom ofthe cigar tube, the higher the stability. SBS is regarded as the goldstandard benchmark for modifying asphalt, with SBS modified asphalthaving a cigar test of 2° C. (3.6° F.) difference. In sharp contrast,GTR modified asphalt will have a 30° F. (16.7° C.) difference or worse.Various embodiments of the present invention provide for stabilizing GTRmodified asphalt with the additives of the present invention so that thecigar test temperature difference for the GTR modified asphalt isgreatly improved

When the additives of the present invention are utilized in making GTRmodified asphalt, or otherwise incorporated into GTR modified asphalt,the cigar test results are a lot better than 30° F. (16.7° C.)difference, specifically less than or equal to 14° C. (25.2° F.), 12° C.(21.6° F.), 10° C. (18° F.), 8° C. (14.4° F.), 6° C. (10.8° F.), 4° C.(7.2° F.), 2° C. (3.6° F.), 1° C. (1.8° F.), or 0.5° C. (0.9° F.)temperature difference using ASTM D 7173. In other words, the additivesof the present invention stabilize GTR in asphalt so that the GTRmodified asphalt now meets the SBS gold standard regarding the cigartest of 2° C. (3.6° F.). In some embodiments, the additive may notrequire the secondary rheology modifying component to stabilize theground tire rubber in asphalt.

As one non-limiting embodiment, the primary rheology modifyingcomponent(s) and the secondary rheology modifying component(s) may bemelted together into a molten liquid phase, mixed, and then formed intosolid form which is now useful as an asphalt additive. As a specificnon-limiting example of this embodiment, melt wax, polymers, andElvaloy® terpolymer, mix and form solid additive. As another specificnon-limiting example of this embodiment, melt wax and Elvaloy®terpolymer, mix and form solid additive.

As a more specific non-limiting embodiment of the above embodiment, theprimary rheology modifying component(s) and the secondary rheologymodifying component(s) may be melt mixed via extrusion, with theextrudate made into solid form which is now useful as an asphaltadditive. As a specific non-limiting example of this embodiment, meltmix via extrusion the polymers, wax and Elvaloy® terpolymer, next formthe extrudate into the solid additive.

As another non-limiting embodiment, the primary rheology modifyingcomponent(s) and the secondary rheology modifying component(s) may bemelted together into a molten liquid phase, mixed, and then formed intosolid form. This additive in solid form may be combined with additionalprimary rheology modifying component(s) and/or secondary rheologymodifying component(s) and utilized as an asphalt additive. It should beappreciated the formed solid additive and additional rheology modifyingcomponent(s) may be combined prior to contacting with asphalt, added toasphalt simultaneously, or added to asphalt consecutively. As a specificnon-limiting example of this embodiment, melt wax and polymers mix andform into pellets, then combine these pellets with Elvaloy pellets inthe asphalt blend tank.

Some embodiments of the present invention will melt the primary andsecondary rheology modifying components together at the same time. Otherembodiments will first melt the primary rheology modifying component(s),and then introduce the secondary rheology modifying component(s) to themelted primary rheology modifying component(s). The secondary rheologymodifying component(s) may or may not be melted at the time of theintroduction. As a non-limiting example, utilizing a twin screwextruder, the primary rheology modifying component(s) (as a non-limitingexample a PAO and an Elvaloy terpolymer) are introduced at the front endof the extruder. The secondary rheology modifying component may beintroduced at the front end of the extruder along with the primaryrheology modifying component(s) (as a non-limiting example a wax) or maybe introduced after the front end of the extruder (generally at the endof the first screw/beginning of the second screw) to join the alreadymelted primary rheology modifying component(s).

As a more specific non-limiting embodiment of the above embodiment, theprimary rheology modifying component(s) and the secondary rheologymodifying component(s) may be melt mixed via extrusion, with theextrudate then formed into solid form. This additive in solid form maythen be combined with additional primary rheology modifying component(s)and/or secondary rheology modifying component(s) and utilized as anasphalt additive. It should be appreciated the formed solid additive andadditional rheology modifying component(s) may be combined prior tocontacting with asphalt, added to asphalt simultaneously, or added toasphalt consecutively. As a specific non-limiting example of thisembodiment, melt mix the polymers and wax via extrusion, then pelletizethe extrudate, then combine these pellets with Elvaloy® terpolymer inthe asphalt blend tank.

As even another non-limiting embodiment, the primary rheology modifyingcomponent(s) and the secondary rheology modifying component(s) may bemicronized via high shear grinding to form the asphalt additive. As aspecific non-limiting example of this embodiment micronize via highshear grinding polymer, wax and Elvaloy to form the asphalt additive.The components may be combined before the high shear grinding andsubjected to the grinding together, or may be subjected to the grindingseparately and combined afterwards.

As even another non-limiting embodiment, the asphalt additive may beformed by micronizing the primary rheology modifying component(s) viahigh shear grinding, without the need for the secondary rheologymodifying component(s). It is believed that the micronized primaryrheology modifying component(s) will sufficiently disperse in asphaltwithout the need for the secondary rheology modifying component. As aspecific non-limiting example of this embodiment, would includemicronizing Elvaloy® terpolymer and adding to the asphalt blend tank.

Should more than one primary rheology modifying component and/orsecondary rheology modifying component be micronized, the components maybe combined before micronizing and subjected to micronizing together, ormay be subjected to micronizing separately and combined afterwards, oradded simultaneously or sequentially to the asphalt after micronizing.

Any suitable micronizing method and apparatus may be utilized to formthe micronized additive of the present invention. Common traditionalmicronization techniques are based on friction to reduce particle size,and such methods include milling, bashing and grinding. A typicalindustrial mill is composed of a cylindrical metallic drum that usuallycontains steel spheres. As the drum rotates the spheres inside collidewith the particles of the solid, thus crushing them towards smallerdiameters. In the case of grinding, the solid particles are formed whenthe grinding units of the device rub against each other while particlesof the solid are trapped in between. Methods like crushing and cuttingare also used for reducing particle diameter, but produce more roughparticles compared to the two previous techniques (and are therefore theearly stages of the micronization process). Crushing employs hammer-liketools to break the solid into smaller particles by means of impact.Cutting uses sharp blades to cut the rough solid pieces into smallerones. There are also cryogenic techniques for micronizing. For example,some methods use supercritical fluids in the micronization process. Themost widely applied techniques of this category include the RESS process(Rapid Expansion of Supercritical Solutions), the SAS method(Supercritical Anti-Solvent) and the PGSS method (Particles from GasSaturated Solutions).

Another embodiment of the present invention provides for the dispersionof the primary rheology modifying component(s) by first micronizingthose components which allows for dispersion of those components intoasphalt without the need for the secondary rheology modifyingcomponent(s). In general additive particles of the present inventionwill be dispersible in asphalt if the particles have a diameter lessthan about 600, 400, 300, 250, 200, 150, 75, 40, or 15 μm (microns), orwill pass through a mesh size of 30, 40, 50, 60, 80, 100, 200, 400, or800 mesh.

Some embodiments of the present invention favor utilizing additive withglycidyl functionality, glycidyl acrylate functionality, or epoxidefunctionality for modifying asphalts with higher asphaltene content,while other embodiments favor utilizing additive with polyolefin(s)(PAO's) for modifying asphalts with lower asphaltene content. Generally,low asphaltene asphalts will have in the range of about 3 to 5 wt %asphaltene content (or less) whereas high asphaltene asphalts will havein the range of about 12 to 15 wt % asphaltene content (or more). Theshould be considered a continuum, with those asphalts with asphaltenecontent in the middle (i.e, between 5 and 12 wt %), utilizing anadditive having a mixture.

Some non-limiting embodiments of the present invention provide formethods of modifying a petroleum asphalt, the method comprising:combining the petroleum asphalt with an additive to form a modifiedasphalt, wherein the additive comprises ground tire rubber and resin,wherein the resin is selected from the group consisting of reactiveelastomeric terpolymers, polymers having glycidyl functionality,polymers having glycidyl acrylate functionality, and polymers havingepoxide functionality.

EXAMPLES

For the Examples “Rheopave 10 XP” (also referred to as Rheopave XP 10)is a melt blended mixture of a wax, polypropylene homopolymer and afunctionalized polymer containing glycidyl methacrylate functionality(Elvaloy terpolymer) in solid form. “Rheopave 100” is a melt blendedmixture of a wax and polypropylene homopolymer in solid form.

For the Examples, production of Rheopave products involve melt blendingvia extrusion for complete dispersion of the components which are wax,PP homopolymer and Elvaloy 4170 for Rheopave 10XP (no Elvaloy inRheopave 100). The resulting Rheopave product is in the physical form ofpellets. The Rheopave pellets are added to hot asphalt base in a stirredvessel at 375 DEG F. and stirred for one hour after addition. Theresultant modified asphalt is then cooled and the various standardizedlaboratory tests are performed according to standard procedures.Rheopave 10XP is generally PP with MFR 20 (35 wt %), Elvaloy 1117 (50 wt%), and CWP 500 PE Wax (15 wt %). Rheopave 100 is generally PP (70 wt %)and wax (30 wt %).

Example 1

Supporting data for asphalt modifier patent based on polyropylenehomo-polymer and polypropylene plus polyethylene co-polymer as primaryrheology agents and specified secondary rheology modifying agents.

TABLE 1 Base Asphalt Base Asphalt plus 4% plus 4% Method Base AsphaltAdditive A Additive B Continuous PG Grade 68.4-24.2 78.9-23.0375.3-23.69 Rotational Visco. at 270 F., cps TP 48 Rotational Visco. at300 F., cps TP 48 Rotational Voisc. at 135 C., cps TP 48 0.56 1280.001030 Dynamic Shear Rheometer: T315 Temperature Pass, C. 67.00 76.0070.00 Phase Angle 68.10 82.00 G* at 10 rad/sec, kPa. 1.62 1.76 G*/sindelta at 10 rad/sec., kPa. 1.27 1.74 1.77 Temperarure Fail, C. 69.0082.00 76.00 Phase Angle 64.80 83.80 G* at 10 rad/sec, kPa. 1.00 0.93G*/sin delta at 10 rad/sec., kPa. 1.10 0.94 Pass/Fail, Temp. C. 83.1075.30 RTFO Residue Tests: Mass Loss, % T240 0.06 0.27 −0.26 DynamicShear Rheometer T315 2.62 Temperature Pass, C. 68.40 76.00 70.00 PhaseAngle 73.30 76.80 G* at 10 rad/sec, kPa. 2.83 4.76 G*/sin delta at 10rad/sec., kPa. 2.95 4.83 Tempersture Fail, C. 82.00 76.00 Phase Angle74.00 79.20 G* at 10 rad/sec, kPa. 1.55 2.35 G*/sin delta at 10rad/sec., kPa. 1.60 2.39 Temperature Pass/Fail, C. 78.90 76.70 PAVResidue Tests: Dynamic Shear Rheometer T315 Temperature, C. 25.00 28.0028.00 Phase Angle 43.00 41.90 G* at 10 rad/sec, kPa. 2590.00 3860.00G*/sin delta at 10 rad/sec., kPa. 1770.00 2580.00 Bending Beam RheometerT313 Temperature Pass, C. −12.00 −12.00 −12.00 Stiffness, 60 s, Mpa104.00 142.00 147.00 M-value, 60 s 0.35 0.31 0.31 Temperature Fail, C.−18.00 −18.00 Stiffness, 60 s, Mpa 283.00 300.00 M-value, 60 s 0.27 0.27Additional Dynamic Shear Rheometer (DSR) Data DemonstratingEffectiveness of PP Compounds in High Temperature Performance GradingPhase Composition, Angle Test Sample Reference % m/m of Additive G*G*/Sind Degrees Temperature, C. Base Valero PG 67-22 3% SB2 in V67-2285% PP (stream 1.00 1.01 84.2 67 1) plus 15% PE 0.73 0.75 75.8 82 Wax 4%SB2 in V67-22 85% PP 1.28 1.31 76.5 76 (stream 1) plus 1.42 1.49 72.0 8215% PE Wax 6% SB2 in V67-22 85% PP 1.14 1.26 64.5 88 (stream 1) plus 15%PE Wax 3% SB3 in V67-22 85% PP (stream 0.84 0.85 82.5 76 2) plus 15% PEWax 3% SB4 in V67-22 85% PP (stream 1.64 1.66 81.3 70 2) plus PE Wax0.81 0.82 84.4 76 3% SB5 in V67-22 100% PP 1.66 1.67 83.0 70 (Stream 2)0.87 0.88 84.0 76 3% SB6 in V67-22 42.5% PP Wax 1.76 1.78 82.6 70Stream 1) plus 0.97 0.98 82.5 76 42.5% PP Wax 1.95 1.97 81.4 70 (stream2) plus 15% PE Wax Notes: 1. Additive A = 85% Resin plus 15% PEBy-Product Wax and Continuous PG grade escalated from PG 68.4-24.2 to PG78.9-23.03. This represents binder PG improvement of 2 full grades. 2.Additive B = 80% Resin plus 20% Micro-Wax and Continuous PG gradeescalated from PG 68.4-24.2 to PG 75.3-23.9. This represents a full onePG improvement in binder grade. A marginal incresae in Additive B willmeet the PG 76-22 Grade. 3. Unlike Fischer-Tropsch Waxes and otherPlastomeric additives, the Low temperature grading is not negativelyimpacted. 4. The Rotational Viscosity of the modified Asphalt blends areless than 50% of the specified maximum viscosity of 3,000 cps at 135 C.This substantial lower viscosity will reduce the viscosity of theaggregate mix in a corresponding manner and will result in Warm MixAsphalt benefits.

Example 2

The follow data shows PP compound (Rheopave 100) improving theseparation stability in Crumbed Rubber Asphalt formulations

TABLE 2 CIGAR CIGAR TUBE ORIGINAL BLEND TUBE TOP BOTTOM DSR @ 76° C. RV@ 300° F. 10% GTR MESH 80 139.4° F. 163.5° F. — — IN V67-22 10% GTR MESH80 151.5° F. 153.5° F. — — IN V67-22 + 1% RETEST: RESTES: RHEOPAVE 100150.7° F. 152.9° F. 10% GTR MESH 40 135.1° F. 161.6° F. — — IN V67-2210% GTR MESH 40 145.7° F. 160.0° F. G*Sin(δ) = 1740 cps IN V67-22 + 1%SBS 2.33 KPa Phase Angle = 75.6° 10% GTR MESH 40 150.1° F. 149.5° F.G*Sin(δ) = 1550 cps IN V67-22 + 1% 2.07 KPa RHEOPAVE 100 Phase Angle =77.4° 10% GTR MESH 40 140.0° F. 163.2° F. G*Sin(δ) = 1445 cps INV67-22 + 0.5% 1.91 KPa RHEOPAVE 100 Phase Angle = 79.0° 10% GTR MESH 40149.4° F. 150.3° F. G*Sin(δ) = 1630 cps IN V67-22 + 0.5% 2.39 KPa SBS +0.5% Phase Angle = RHEOPAVE 100 76.3° SFMC ARB-5 126.0° F. 145.0° F. — 550 cps SFMC ARB-5 + 0.5% 130.1° F. 145.5° F. — — RHEOPAVE 100 SFMCARB-5 + 1% 136.0° F. 138.8° F. —  795 cps RHEOPAVE 100

Example 3

TABLE 3 Hamburg Wheel Rut Depth @ 20,000 Passes, mm Total Passes to 12.5mm Rut Depth Mix Type Sample 1 Sample 2 Average Sample 1 Sample 2Average PG 76-22 6.392 5.549 5.971 95,130 173,593 134,362 GTR 8.7929.727 9.260 54,328 49,580 51,954

Based upon the Hamburg testing criteria set forth by the TexasDepartment of Transportation, shown in Table 4, both samples meet theHamburg criteria for a PG 76 and above high temperature grade. Strippinginflection points were not observed for either mixture.

TABLE 4 Minimum # of Passes @ 12.5 mm High Temperature Binder Rut Depth,Tested @ Grade 122° F. PG 64 or Lower 10,000 PG 70 15,000 PG 76 orHigher 20,000

Example 4

TABLE 5 provides the results of a 10% GTR FORMULATION IN 67-22,subjected to various testing.

Project Title/Specs: 10% GTR FORMULATION IN 67-22 Rheopave 10 XP at 0.5%Sample 1 Sample 2 Specification Sample ID BASE 67-22 AWI-GAT 10% GTRFORMULA* Continuous PG Grade 69.0-23.1 80.8-22.4 76-22 Full PG 67-2276-22 76-22 Original Binder Tests: Rotational Viscosity, 135 C., —2600.0 <3000 cps Softening Point, F. — 146.2 Dynamic Shear Rheometer T315 Continuous 69.0 83.5 >76 PG Temp Pass 64 82 Phase Angle, degrees86.2 76.8 G* @10 rad/sec, kPa 1.830 1.11 G*/sin delta @10 rad/sec, 1.8301.14 kPa Temp Fail 70 88 Phase Angle, degrees 87.7 80.1 G* @10 rad/sec,kPa 0.880 0.649 G*/sin delta @10 rad/sec, 0.880 0.659 kPa RTFO ResidueTests: MSCR, 64 C., Jnr @ 3.2 kPa 1.973 0.354 <1.0 % Rec. @ 3.2 kPa2.62% 40.97% >35% Diff in Jnr @ 3.2 kPa 9.56% 28.17% <75% Dynamic ShearRheometer T 315 Continuous 69.9 80.8 >76 PG Temp Pass 64 76 Phase Angle,degrees 82.1 69.3 G* @10 rad/sec, kPa 4.67 3.27 G*/sin delta @10rad/sec, 4.71 3.49 kPa Temp Fail 70 82 Phase Angle, degrees 84.4 72.3 G*@10 rad/sec, kPa 2.17 1.87 G*/sin delta @10 rad/sec, 2.18 1.96 kPa PAVResidue Tests: Dynamic Shear Rheometer T 315 Temp Pass — 31 Phase Angle,degrees — 48.7 G* @10 rad/sec, kPa — 1450 G*sin delta @ 10 rad/sec, —1090 <5000 kPa Bending Beam Rheometer T 313 Temp Pass −12 −12 s, 60 s,Mpa 185 112 <300 M-value, 60 s 0.310 0.314 >0.300 Temp Fail −18 −18 s,60 s, Mpa 391 214 M-value, 60 s 0.253 0.260 Notes: *10% 40 Mesh GTR +0.50% Rheopave XP10A + 1% Hydrogreen in 67-22

Example 5

TABLE 6 is a comparison of PG64-22 TO PG76-22TR RHEOPAVE XP10 VS.VESTENAMER 8021 (a cyclo octene polymer), with both subjected to varioustesting. Project Title/Specs: PG64-22 TO PG76-22TR RHEOPAVE XP10A VS.VESTENAMER - MAY 2013 Sample 1 Sample 2 Sample 3 Sample 4 Samplel ID400TR + 1% 400TR + 1% 30AA + 1% 30AA + 1% RHEOPAVE VESTENAMER RHEOPAVEVESTENAMER XP10 XP10 Continuous PG Grade 80.1-23.8 80.7-19.3 79.8-23.380.7-24.2 Full PG 76-22 76-16 76-22 76-22 Original Binder Tests:Rotational Visc, 135 C., cps 4338 4200 3850 3612 CG Top/Bottom, F.Dynamic Shear Rheometer T 315 Continuous PG 83.7 83.4 83.1 83.3 TempPass 82 76 82 82 Phase Angle, degrees 74.2 75.1 74.3 74.3 G* @10rad/sec, kPa 1.12 1.98 1.06 1.94 G*/sin delta @10 rad/sec, kPa 1.16 2.051.100 2.02 Temp Fail 88 82 88 82 Phase Angle, degrees 77.3 78.5 77.477.6 G* @10 rad/sec, kPa 0.667 1.11 0.638 1.10 G*/sin delta @10 rad/sec,kPa 0.684 1.13 0.654 1.13 RTFO Residue Tests: MSCR, 64 C., Jnr/% Rec0.331/47.40% 0.441/33.36% 0.403/ 0.449/30.34% 41.84% Dynamic ShearRheometer T 315 Continuous PG 80.1 80.7 79.8 80.7 Temp Pass 76 76 76 76Phase Angle, degrees 67.0 69.9 66.1 69.4 G* @10 rad/sec, kPa 2.90 3.292.79 3.24 G*/sin delta @10 rad/sec, kPa 3.15 3.50 3.05 3.46 Temp Fail 8282 82 82 Phase Angle, degrees 69.0 73.1 68.5 72.6 G* @10 rad/sec, kPa1.73 1.86 1.69 1.85 G*/sin delta @10 rad/sec, kPa 1.86 1.95 1.82 1.94PAV Residue Tests: Temp Pass −6 −12 −6 −12 s, 60 s, Mpa 46 117 53 99M-value, 60 s 0.361 0.285 0.360 0.310 Temp Fail −12 −18 −12 −18 s, 60 s,Mpa 107 200 113 197 M-value, 60 s 0.314 0.252 0.311 0.283 Notes:Formulas are all 10% GTR + 1% Vestenamer/Rheopave XP10A Additive Ablends meet all Georgia requirements except RV @ 135 C. Vestenamerblends: 400TR - Does not meet RV @ 135 C., phase angle, MSCR and BBR30AA - Does not meet RV @ 135 C., and MSCR

Example 6

Referring now to FIG. 1, there is provided TABLE 7, Separation TestResults for Test Highway using Rheopave 10XP. The evaluating state DOTnoted the workability and compaction of the Rheopave mix and which wassuperior to usual Asphalt Rubber Binder Mixes.

Example 7

Table 8 provides various test results for 82-22 ARB binder.

TABLE 8 82-22 ARB BINDER. LTRC Results Physical Properties Sample Sample(Tests) Sample # 1 # 2 # 3 AVG Rotational Viscosity @ 135° C. (Pa · s) —— — 3.16 Original DSR @ 82° C. (G*/Sinδ) 1.74 1.78 — 1.76 Original DSR-Phase Angle @ 82° C. 76.5 76.2 — 76.4 RTFO DSR @ 82° C. (G*/Sinδ) 3.883.83 — 3.86 RTFO DSR- Phase Angle @ 82° C. 67.0 67.3 — 67.2 % ElasticRecovery @ 25° C., 10 cm elongation 64.0 64.0 — 64.0 MSCR % R_(3.2) @64° C. 59.250 59.218 — 59.234 MSCR J_(nr,3.2) @ 64° C. 0.105 0.109 —0.107 MSCR % R_(3.2) @ 67° C. 52.017 51.719 — 51.868 MSCR J_(nr,3.2) @67° C. 0.173 0.181 — 0.177 PAV DSR @ 25° C. (G*Sinδ) 2470 2570 — 2520PAV DSR- Phase Angle @ 25° C. 41.4 41.0 — 41.2 BBR Creep Stiffness, S,Mpa @ −12° C. 109 112 103 108 BBR Creep Slope, m Value @ −12° C. 0.3110.313 0.310 0.311

Example 8

Referring now to FIG. 2, there is provided TABLE 9, showing various testresults for PG67-22 Base Asphalt Upgraded to PG76-22 GTR with MSCRSpecification.

Example 9

TABLE 10 provides various test results for PG67-22 Base Asphalt Upgradedto PG 76-22 GTR with MSCR Specification.

TABLE 10 PG67-22 Base Asphalt Upgraded to PG 76-22 GTR with MSCRSpecification 9% GTR Formula with Rheopave 10 Property XP Target RV at135 C. (cP) 2850 3000 Max Original DSR at 76 C. Phase Angle (Deg) 71.6<75 G*/Sin (kPa) 1.97 Min 1.0 RTFO DSR at 76 C. Phase Angle (Deg) 63.5G*Sin (kPa) 4.83 Min 2.2 Fail Temp (Deg C.) 85.1 Min 76 PAV DSR at 76 C.Phase Angle 44.1 MSCR at 64 C. Jnr/% Rec 0.208/62.98% % Rec >50% BBR at−12 Deg C. Tm Value (Mpa) 0.334 Min 0.30 Stiffness (Mpa) 152 Max 300 BBRat −18 Deg C. m-Value (Mpa) 0.283 Min 0.30 Stiffness (Mpa) 273 Max 300Continuous PG: 83.4-26.0 76-22 PG Grade: 82-22 76-22

Example 10

Referring now to FIG. 3 there is provided TABLE 11 showing testing datefor the PG (ARB)-22 TEST SECTION completed for a state DOT, and also toFIGS. 4A and 4B providing Table 12 (Parts 1 and 2), and to FIGS. 5A and5B (Providing Table 13 (Parts 1 and 2), showing certification for theRheopave modified asphalt. The evaluating state DOT noted theworkability and compaction of the Rheopave mix and which was superior tousual Asphalt Rubber Binder Mixes.

The present disclosure is to be taken as illustrative rather than aslimiting the scope or nature of the claims below. Numerous modificationsand variations will become apparent to those skilled in the art afterstudying the disclosure, including use of equivalent functional and/orstructural substitutes for elements described herein, use of equivalentfunctional couplings for couplings described herein, and/or use ofequivalent functional actions for actions described herein. Anyinsubstantial variations are to be considered within the scope of theclaims below.

The invention claimed is:
 1. An asphalt comprising: a first componentcomprising a petroleum asphalt; and, a second component comprisingparticles formed from a melted mixture of a resin and a binder; wherein,the second component is dispersed within the first component; whereinthe resin is polypropylene homopolymer; and, wherein the bindercomprises a terpolymer comprising at least one of glycidylfunctionality, glycidyl acrylate functionality, or epoxidefunctionality.
 2. The asphalt of claim 1, wherein the binder comprises aterpolymer comprising an ethylene-butyl acrylate-glycidyl methacrylate.3. A method of treating a petroleum asphalt, the method comprising:contacting a petroleum asphalt with particles formed from a meltedmixture of a resin component and a binder component to form a treatedasphalt, wherein the resin is polypropylene homopolymer; and, whereinthe binder comprises a terpolymer comprising at least one of glycidylfunctionality, glycidyl acrylate functionality, or epoxidefunctionality.
 4. The method of claim 3, wherein the binder comprises aterpolymer comprising an ethylene-butyl acrylate-glycidyl methacrylate.5. An asphalt comprising: a first component comprising a petroleumasphalt; a second component comprising particles formed from a meltedmixture of a resin and a binder; and, a third component dispersed in theasphalt selected from the group consisting of ground tire rubber andpolymers of styrene and butadiene, wherein the resin is polypropylenehomopolymer; and, wherein the binder comprises a terpolymer comprisingat least one of glycidyl functionality, glycidyl acrylate functionality,or epoxide functionality.
 6. The method of claim 5, wherein the bindercomprises a terpolymer comprising an ethylene-butyl acrylate-glycidylmethacrylate.
 7. A method of modifying a petroleum asphalt, the methodcomprising: combining the petroleum asphalt with a first component and asecond component, wherein the first component comprises particles formedfrom a melted mixture of a resin and a binder; and, the second componentis selected from the group consisting of ground tire rubber and polymersof styrene and butadiene, wherein the resin is polypropylenehomopolymer; and, wherein the binder comprises a terpolymer comprisingat least one of glycidyl functionality, glycidyl acrylate functionality,or epoxide functionality.
 8. The method of claim 7, wherein the bindercomprises a terpolymer comprising an ethylene-butyl acrylate-glycidylmethacrylate.